CN1278760C - Preparation method of catalyst for selective catalytic reduction of nitrogen oxide - Google Patents

Preparation method of catalyst for selective catalytic reduction of nitrogen oxide Download PDF

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CN1278760C
CN1278760C CNB011376228A CN01137622A CN1278760C CN 1278760 C CN1278760 C CN 1278760C CN B011376228 A CNB011376228 A CN B011376228A CN 01137622 A CN01137622 A CN 01137622A CN 1278760 C CN1278760 C CN 1278760C
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catalyst
weight
carrier
tungsten
dead catalyst
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CN1354039A (en
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崔京一
李相昊
申哲雨
安晙成
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SK Innovation Co Ltd
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SK Holdings Co Ltd
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    • B01J35/19—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P29/00—Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
    • Y10S502/506—Method of making inorganic composition utilizing organic compound, except formic, acetic, or oxalic acid or salt thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
    • Y10S502/514—Process applicable either to preparing or to regenerating or to rehabilitating catalyst or sorbent

Abstract

Disclosed are a catalyst for selective catalytic reduction of nitrogen oxides and a method for preparing the same. The catalyst is prepared using a spent catalyst discharged from a hydro-desulfurization process of an oil refinery in which the spent catalyst comprises vanadium, nickel, molybdenum and sulfur component on alumina, and a tungsten-impregnated support. The catalyst prepared in accordance with the present invention is very advantageous in terms of excellent selective removal effect of nitrogen oxides as well as better poisoning resistance to sulfur oxides.

Description

The Preparation of catalysts method that is used for the SCR of nitrogen oxide
Background of invention
1. invention field
Present invention relates in general to be used for the catalyst of SCR of nitrogen oxide and the method for preparing above-mentioned catalyst.More specifically, the present invention relates to be used for the Preparation of catalysts method of the SCR of nitrogen oxide, the catalyst poisoning that this method has good nitrogen oxide removal efficient, high high-temp stability and chemical stability and can prevent from contained various inorganic, organic dust and sulphur compound in the waste gas are produced, the carrying alumina build dead catalyst recirculation that this catalyst can be discharged by the hydrodesulfurization of oil plant and preparing.
2. the description of prior art
Usually, the factory of consumption fossil fuel such as power plant and chemical plant can produce nitrogen oxide (NO inevitably x).Find that at present nitrogen oxide is direct pollution sources, as acid rain and smog.Now, most countries comprises that Korea S's strictness forbids that nitrogen oxides emission exceeds the permission standard level.Therefore, need to study the technology of from waste gas, removing nitrogen oxide in combustion system.
Simultaneously, for removing the discharging of nitric oxide source, there is reaction generation under the excess air condition in this nitric oxide source by nitrogen and oxygen in the high-temp combustion device, attempt improving burning condition now, as burning of hypoxemia amount and waste gas circulation.Yet nitrogen oxide can not only be removed by improving combustion technology fully, therefore needs the various aftertreatment technologys of research and development, can be by removing nitrogen oxide in the waste gas by this technology.
Usually will be used for effectively removing nitrogen oxide (NO x) technology be divided into the selective catalytic reduction reaction (SCR) that uses catalyst and reducing agent, only use reducing agent not have selection of catalysts non-catalytic reduction reaction (SNCR), can control the low-NO of burning condition in the combustion furnace xCombustion furnace technology etc.Wherein, consider the factor such as generation, elimination efficiency, operating cost of secondary pollution, SCR is considered to remove the effective technology of nitrogen oxide.By using the SCR technology, the removal efficient of nitrogen oxide reaches 90% or higher and its durable time is longer, can use about 2-5.In addition, described technology is advanced technically, because can remove poisonous dioxin in the incinerator with nitrogen oxide.
According to the outer shape of catalyst, the catalyst that is used for SCR can be divided into extruding honeycomb type catalyst, metal sheet type catalyst, and pellected catalyst.At present, extruding honeycomb type and metal sheet type catalyst have been widely used in steam power plant and incinerator.As catalyst carrier is titanium dioxide, aluminium oxide, silica, zirconia etc., and catalytic component mainly comprises the oxide of reactive metal such as vanadium, molybdenum, nickel, tungsten, iron and copper, and comprises that other reactive metal composition is to add wide temperature range and to improve the durability of catalyst.
The catalyst that becomes known for SCR recently can be made the catalyst that contains the crystalline phase oxide by with catalyst component such as vanadium, molybdenum, nickel and tungsten dipping inorganic oxide carrier such as titanium dioxide, aluminium oxide, silica and zirconia with after-baking.
In this respect, US5,827,489 disclose the Preparation of catalysts method that is used for SCR, this catalyst is by with catalyst component such as vanadium, molybdenum, nickel and tungsten dipping inorganic oxide carrier such as titanium dioxide, aluminium oxide, silica and zirconia, the catalyst made from after-baking that contains the crystalline phase oxide.Carrier that is used for SCR that uses in this patent and catalyst component have excellent anticatalyst poisoning characteristic and help freely controlling the specific area of reactive metal quantity, catalyst and the catalyst that pore size has optimum performance with preparation sulfur oxide, have added an amount of sulfate in this catalyst.On the other hand, this catalyst needs high preparation cost, because need to prepare and mix by the catalyst manufacture method as the homogenous material (or precursor) of carrier and catalyst.
Simultaneously, in fact oil plant uses hydrodesulfurization to remove contained sulphur component in the crude oil, and dead catalyst is as byproduct and reject.Yet if dead catalyst does not recycle, therefore processing cost can improve, and considers it is disadvantageous from economic aspect.
In this respect, open No.95-72277 of Korean Patent pending trial and U.S. Pat 6,171,566 disclose the recirculation of the dead catalyst of being discharged by the oil plant hydrodesulfurization.It is more excellent that the catalyst that is used for SCR that recirculation by above-mentioned dead catalyst prepares is compared in the following aspects with the catalyst for preparing by the homogenous material integration of operation: preparation cost is low, the anticatalyst poisoning characteristic intrinsic to sulfur oxide, and contain high-load metal component, this metal component has very strong nitrogen oxide reduction activity.
Yet when using dead catalyst separately in the SCR at nitrogen oxide, wherein contained reactive metal composition is not immersed in the carrier hole equably, or on its surface, but be lumps, therefore reduced catalytic performance.The shortcoming that above-mentioned patent exists is with excessive levels rather than with requirement impregnation catalyst active component.And existence can reduce a spot of other metal ingredient and the excessive sulphur compound of catalytic performance, and the dead catalyst from different discharge pipe discharges has different characteristics after hydrodesulfurization, and it is difficult therefore being used for extensive catalytic reaction.Only use under the situation of preliminary treatment dead catalyst in the Preparation of catalysts process of the SCR that is used for nitrogen oxide, Zhi Bei catalyst can not show the performance of enough satisfaction like this.And, because the carrier in the dead catalyst mainly comprises aluminium oxide, when in a large amount of application of discharging sulphur components and greasy filth, using catalyst because catalyst poisoning may take place in physical absorption or chemical reaction.
Summary of the invention
According to the present invention, the dead catalyst of discharging in the oil plant hydrodesulfurization has been carried out intensive research, the present invention is intended to avoid the problem that runs in the prior art, found that the Preparation of catalysts method of caltalyst (catalyst body) form of the SCR that is used for nitrogen oxide, this catalyst has excellent performance and durability, and the preparation cost of dead catalyst is low.
Therefore, the purpose of this invention is to provide the method for catalyst that a kind of preparation is used for the SCR of nitrogen oxide, this catalyst has excellent nitrogen oxide removal effect and anticatalyst poisoning performance.
Another object of the present invention provides the method that a kind of recirculation by the dead catalyst of discharging in the oil plant hydrodesulfurization prepares the catalyst of the SCR that is used for nitrogen oxide.
A further object of the present invention provides a kind of catalyst of the SCR that is used for nitrogen oxide for preparing by the recirculation of the dead catalyst of discharging in the oil plant hydrodesulfurization.
According to the present invention, the method for the catalyst of the SCR that a kind of preparation is used for nitrogen oxide is provided, may further comprise the steps:
A) dead catalyst of discharging in the oil plant hydrodesulfurization is carried out preliminary treatment, this dead catalyst contains the vanadium of 1-30 weight % on aluminium oxide, the nickel of 1-20 weight %, the sulphur component of the molybdenum of 1-20 weight % and 1-15 weight % promptly washes with water subsequently by the above-mentioned dead catalyst of heat treatment
B) a kind of tungsten of 1-15 weight % that uses on carrier matrix of preparation floods the carrier that forms, and described carrier is selected from the group of being made up of aluminium oxide, titanium dioxide, silica, zeolite and composition thereof;
C) pretreated dead catalyst is pulverized, powdery dead catalyst and the carrier that tungsten floods are carried out wet mixed equably adding under entry and the sour condition subsequently;
D) said mixture is dewatered to remove excess water wherein and not have impregnated reactive metal;
E) dry dewatered mixture, the mixture behind the mill-drying subsequently; And
F) mixture after the mixture behind the crush and grind maybe will grind is applied on the structure, and subsequent drying and calcining form caltalyst.
Description of drawings
Also can more be expressly understood above and other objects of the present invention, characteristic and other advantage in conjunction with the accompanying drawings according to following detailed.
Fig. 1 is to use dead catalyst of the present invention preparation to be used for the schematic diagram of method of catalyst of the SCR of nitrogen oxide.
Detailed Description Of The Invention
" catalyst " that be used for the SCR of nitrogen oxide among the present invention should have the active metallic content of aequum, carrier specific area and the pore size of regulation, and under the severe test condition, show excellent properties. Usually, contain the long-pending catalyst of excessive reactive metal and small specific surface and have excellent nitrogen oxide removal efficient but the active temperature narrow range. Another kind of situation, the catalyst that contains a small amount of reactive metal and bigger serface then low the and active temperature range widens of nitrogen oxide removal efficient to high temperature.
Referring to Fig. 1, it has shown the method for the preparation of the catalyst of SCR of the present invention.
The present invention utilizes the dead catalyst of discharging in the oil plant hydrodesulfurization. Dead catalyst contains the vanadium of 1-30 % by weight at alumina support, the nickel of 1-20 % by weight, and the sulphur component of the molybdenum of 1-20 % by weight and 1-15 % by weight, the specific area of this catalyst are 30-200m2/ g and pore size are 100-300 .
Generally, the surface of dead catalyst is polluted in conjunction with various impurity by oil, carbon and a part of sulphur in hydrodesulfurization. Be to remove mentioned component, preferably under 300-400 ℃ with dead catalyst heat treatment 3-5 hours. In above-mentioned heat treatment temperature, namely under the standard processing conditions, can effectively remove carbon and a part of sulphur (particularly carbon). Subsequently, preferably in intermittent aeration is bathed (aeration bath), wash about 1 hour of heat treated dead catalyst with water and be reduced to a certain content with the excess metal composition of removing the sulphur component and will be accumulated in the dead catalyst. For ease of removing excessive metal ingredient, can choose wantonly with acid such as the oxalic acid treatment dead catalyst.
Irrelevant with above-mentioned pre-treatment step, below preparation and carrier with the tungsten dipping is provided. This carrier is selected from aluminium oxide with bigger serface, titanium dioxide, silica, zeolite and composition thereof. In the carrier that has flooded tungsten, with ratio tungsten dipping on carrier matrix of 1-15 % by weight. Particularly, preferred above-mentioned aluminium oxide uses the titanium dioxide that gamma-alumina and use have the anatase crystal structure. Therefore, the specific area of the carrier of tungsten dipping is 50-400m2/ g and pore size are 150-250 .
Pretreated dead catalyst is ground into Powdered to be suitable for the even mixing in the following step.
The carrier of the catalyst after the aforesaid pulverizing and above-mentioned tungsten dipping is wet mixed under the condition that adds entry and acid. In by above-mentioned wet mixed step, the reactive metal composition that contains in the dead catalyst is dissolved out and is impregnated into equably on the carrier of own tungsten dipping. Simultaneously, by weight, the carrier of dead catalyst and tungsten dipping carries out the ratio preferred 50 of wet mixed: 50-70: 30. When the amount of dead catalyst was lower than 50 % by weight, the amount of reactive metal is incited somebody to action very low and specific area is excessive. On the other hand, when dead catalyst surpassed 70 % by weight, the metal ingredient that exists in the mixture was excessive and specific area is too low.
Above-mentioned pulverizing and wet mixed step can be in the ball-milling reaction devices about 3-4 hour. In the wet mixed step, add suitable quantity of water and acid to obtain the muddy mixture.
In dead catalyst, usually there is the crumby reactive metal composition of a large amount of inhomogeneous dippings in the hole of aluminium oxide or on the surface. According to the present invention, use the excess metal composition that contains in the acid dissolving dead catalyst. Above-mentioned dissolved reactive metal redistributes on the carrier of tungsten dipping. In other words, the reactive metal composition is dissolved in the acid so that the aluminium oxide of dead catalyst has larger specific area and excessive reactive metal to be adsorbed to has in the carrier hole than the tungsten dipping of bigger serface. Acid can lytic activity metal such as vanadium, nickel, molybdenum and organic principle. Thus, can use in right amount acid because the excessive adding of acid will cause dissolved oxygen alumina supporter and metal. According to metal ingredient contained in the dead catalyst, above-mentioned acid is for example used oxalic acid and in the preferred adding of dead catalyst 1-5 % by weight.
After the wet mixed step, at about 1471kPa (15kg/cm2) use under the pressure filter press make slurry mixture evenly dehydration obtain thus dewatered cake to remove excessive moisture content and metal ingredient.
Above-mentioned dewatered mixture is preferably lower dry to remove moisture content wherein, to be suitable for the Kaolinite Preparation of Catalyst body at 100-200 ℃. The mixture of drying is ground to the suitable particle diameter that is suitable for preparing extrusion pressing type or structure application type caltalyst, preferred 200 μ m or less.
Mixture after above-mentioned drying and the grinding can be squeezed into, preferred honeycomb type, or coat on the works, preferably under 100-200 ℃, more preferably dry under 100-120 ℃, preferably calcined 3 hours down or the longer time then at 450-550 ℃, obtain catalyst build catalyst thus.The preferred foaming metal (sparkling metals) that uses, for example metal sheet type, or pottery, for example cordierite is as the said structure thing.
According to the present invention, the preferred catalyst of the SCR that is used for nitrogen oxide of preparation as mentioned above comprises metal ingredient and carrier, wherein metal ingredient contains the tungsten, the sulphur composition of 1-10 weight % of nickel, 1-10 weight % molybdenum and 1-15 weight % oxide form of vanadium, the 1-10 weight % of 1-10 weight %, and carrier comprises aluminium oxide or aluminium oxide and a kind of mixture that is selected from following one group of material: titanium dioxide, silica, zeolite and composition thereof.And the specific area of catalyst is 50-150m 2/ g and pore size are 150-250 .
The present invention may be better understood according to following examples, and these embodiment only propose to be used to explain, and do not represent to limit the scope of the invention.
The comparative example 1
With a kind of dead catalyst with specific composition of discharging by the oil plant hydrodesulfurization, 400 ℃ of following heat treatments 3 hours to remove carbon and sulphur component wherein and to wash with water to remove excessive reactive metal composition and sulphur component wherein.Then, with dead catalyst 100 ℃ dry 3 hours and down 450 ℃ of calcinings 3 hours down, this sentences " catalyst A " expression.The composition of use XRF and ICP methods analyst catalyst A also will the results are shown in the following table 1.
The performance test of the nitrogen oxide reduction catalytic activity of catalyst A is to have 500ppm nitric oxide (NO) and 500ppm ammonia (NH 3), the gaseous state hourly space velocity is 100,000/hr, and reaction temperature with the speed of 5 ℃/min by carrying out under the stringent condition that raises in 30 ℃ of-500 ℃ of scopes.The results are shown in the following table 1.
Embodiment 1
The dead catalyst that 500g and comparative example 1 are identical is 400 ℃ of following heat treatments 3 hours and use the 500g water washing.The dead catalyst of as above handling was descended dry 3 hours at 100 ℃, pulverize then.
The ammonium metatungstate adding is had in the metatitanic acid mud that solids content is 20-25 weight %, mix, wherein with the solid weight meter of mud, add the ammonium metatungstate of 5 weight %, subsequently 550 ℃ of heat treatments 2 hours.The specific area that the BET method is measured the titania support of tungsten dipping is 100m 2/ g, and have the anatase crystal structure.
The dead catalyst that 350g is pulverized and the titanium dioxide of 150g tungsten dipping also add 500g water and 8g oxalic acid wet mixed in the ball-milling reaction device.Next step, with mixture at 1471kPa (15kg/cm 2) pressure filters down, 120 ℃ dry 24 hours down, and to grind to form particle diameter be 150 μ m.Then, calcine 3 hours acquisition powder catalysts down, be referred to as " catalyst B " at 450 ℃.The method identical with comparative example 1 carried out the performance test of composition analysis and nitrogen oxide reduction catalytic activity.The results are shown in the following table 1.
Embodiment 2
Except that the titanium dioxide wet mixed of dead catalyst that 250g is pulverized and 250g tungsten dipping, prepare catalyst C with embodiment 1 same procedure.
The method identical with comparative example 1 carried out the performance test of composition analysis and nitrogen oxide reduction catalytic activity.The results are shown in the following table 1.
Table 1
Catalyst Form (weight %) Specificity of catalyst Catalyst performance
V Ni Mo S Al Ti+W Specific area (m 2/g) Maximum activity (%) Field of activity (℃) 1
A 9.2 4.7 3.9 4.2 33.1 - 72 84 -
B 6.5 1.4 2.9 2.3 26.5 19.5 81 98 230-330
C 4.6 1.0 1.1 2.2 19.6 31.8 84 100 210-450
Note: 1: have 90% or more highly active scope
As above shown in the table, catalyst B and C have more excellent catalytic performance and wideer temperature range than catalyst A.
Embodiment 3-5
Prepare catalyst D with embodiment 1 same procedure, E and F, difference is to use respectively to be had specific area and is 200m 2The aluminium oxide of/g (embodiment 3) uses specific area to be 300m 2The silica of/g (embodiment 4) and to have specific area be 300m 2The zeolite of/g (embodiment 5), replacement of titanium dioxide is as the carrier of dipping tungsten.
Adopt XRF and ICP method respectively to catalyst D, E and F carry out composition analysis also with the results are shown in Table 2.
Catalyst D, the performance test of E and F is to have 500ppm nitric oxide (NO) and 500ppm ammonia (NH 3), the gaseous state hourly space velocity is 100,000/hr, and reaction temperature with the speed of 5 ℃/min by carrying out under the stringent condition that raises in 30 ℃ of-500 ℃ of scopes.The results are shown in the following table 2.
Table 2
Catalyst Form (weight %) Specificity of catalyst Catalyst performance
V Ni Mo S Al Other carrier+tungsten Specific area (m 2/g) Maximum activity (%) Field of activity (℃) 1
D 2 6.5 1.4 2.9 2.3 26.5 19.4 88 95 320-400
E 3 6.5 1.4 2.9 2.3 26.5 19.5 92 92 330-410
F 4 6.5 1.4 2.9 2.3 26.5 19.3 97 93 330-430
Note: 1: have 90% or more highly active scope;
2: other carrier is an aluminium oxide;
3: other carrier is a silica; And
4: other carrier is a zeolite.
As above show the result as seen, catalyst D, E and F have excellent catalytic performance in very wide temperature range.
The comparative example 2
The method preparation identical with comparative example 1 catalyst A is used for the material of caltalyst, and difference is not for calcining.With the material of 46 weight %, 42 weight % water, 1 weight % light mineral oil, 4 weight % methylcellulose, 3 weight % glass fibres and 4 weight % kaolin mix, and mediate and be squeezed into to have the cellular of 25 structure cells.With this melikaria 120 ℃ down dry 24 hours and 450 ℃ down calcining obtained catalyst G in 3 hours, adopt XRF and its composition of ICP methods analyst.
The nitrogen oxide reduction catalytic activity performance test of catalyst G is to have 500ppm nitric oxide (NO) and 500ppm ammonia (NH 3), the gaseous state hourly space velocity is 5,000/hr, and reaction temperature with the speed of 5 ℃/min by carrying out under the stringent condition that raises in 30 ℃ of-500 ℃ of scopes.The results are shown in the following table 3.
Embodiment 6
The method preparation identical with the catalyst B of embodiment 1 is used for the mixed material of caltalyst, and difference is not for calcining.Mixed material is made cellular acquisition catalyst H, and the method identical with comparative example 2 carried out composition analysis and performance test.The results are shown in Table 3.
Embodiment 7
The method preparation identical with the catalyst C of embodiment 2 is used for the mixed material of caltalyst, and difference is not for calcining.Mixed material is made cellular acquisition catalyst I, and the method identical with comparative example 2 carried out composition analysis and performance test.The results are shown in Table 3.
Table 3
Catalyst Form (weight %) Specificity of catalyst Catalyst performance
V Ni Mo S Al Ti W Specific area (m 2/g) Maximum activity (%) Field of activity (℃) 1
G 9.0 4.5 3.3 3.6 32.0 - - 70.0 82 -
H 6.3 1.2 2.7 3.6 25.1 15.3 1.0 79.5 95 280-380
I 4.1 1.0 1.3 3.6 17.7 26.2 1.7 83.5 98 270-430
Note: 1: have 90% or more highly active scope
As mentioned above, the catalyst of the SCR that is used for nitrogen oxide prepared according to the methods of the invention has excellent nitrogen oxide removal effect and sulfur oxide is not produced catalyst poisoning.In addition, thus can to recycle be favourable to dead catalyst economically.
The present invention has been described in the mode of explaining in the front, is appreciated that use therein term is the character that is used to describe and do not represent any restriction.Can make many improvement of the present invention and variation according to above-mentioned instruction.Therefore, be appreciated that in claims scope that the present invention does not need to describe in detail and can implement.

Claims (13)

1. be used for the Preparation of catalysts method of nitrogen oxide SCR, may further comprise the steps:
A) also wash with water subsequently by heat treatment, the dead catalyst of discharging in the oil plant hydrodesulfurization is carried out preliminary treatment, this dead catalyst contains the vanadium of 1-30 weight % on aluminium oxide, the nickel of 1-20 weight %, the sulphur component of the molybdenum of 1-20 weight % and 1-15 weight %;
B) preparation is a kind of uses the tungsten in carrier 1-15 weight % to flood the carrier that forms, and described carrier is selected from the group of being made up of aluminium oxide, titanium dioxide, silica, zeolite and composition thereof;
C) pretreated dead catalyst is pulverized, carry out wet mixed equably at the carrier that adds under entry and the sour condition Powdered dead catalyst and tungsten dipping subsequently, wherein the mixed proportion of dead catalyst and tungsten impregnated carrier is 50 by weight in the step c): 50-70: 30;
D) said mixture is dewatered to remove excess water wherein and not have impregnated reactive metal;
E) dry dewatered mixture, the mixture behind the mill-drying subsequently; And
F) mixture after the mixture behind the crush and grind maybe will grind is applied on the works, and subsequent drying and calcining form caltalyst.
2. the process of claim 1 wherein that the specific area of dead catalyst is 30-200m 2/ g and pore size are 100-300 .
3. the process of claim 1 wherein that the specific area of carrier of tungsten dipping that will mix with dead catalyst is 50-400m 2/ g and pore size are 150-250 .
4. the process of claim 1 wherein that the alumina support that provides in the step b) made by gamma-alumina.
5. the process of claim 1 wherein that the titania support that provides in the step b) has the anatase crystal structure.
6. the process of claim 1 wherein that the acid in the step c) is oxalic acid, and be 1-5 weight % in its consumption of dead catalyst.
7. the process of claim 1 wherein that works is by foaming metal or ceramic making.
8. the process of claim 1 wherein that the heat treatment of step a) is to carry out 3-5 hour under 300-400 ℃.
9. the process of claim 1 wherein that the drying of step f) carries out under 100-120 ℃.
10. the process of claim 1 wherein that the calcining of step f) is to carry out 3 hours or longer under 450-550 ℃.
11. catalyst according to the SCR that is used for nitrogen oxide of claim 1 preparation.
12. the catalyst of claim 11, wherein this catalyst comprises metal ingredient and carrier, wherein metal ingredient contains the tungsten, the sulphur composition of 1-10 weight % of nickel, 1-10 weight % molybdenum and 1-15 weight % oxide form of vanadium, the 1-10 weight % of 1-10 weight %, and carrier comprises aluminium oxide or aluminium oxide and a kind of mixture that is selected from following one group of material: titanium dioxide, silica, zeolite and composition thereof.
13. the catalyst of claim 11, wherein the specific area of this catalyst is 50-150m 2/ g and pore size are 150-250 .
CNB011376228A 2000-09-27 2001-09-27 Preparation method of catalyst for selective catalytic reduction of nitrogen oxide Expired - Lifetime CN1278760C (en)

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